Spreading of agricultural sprays on plant surfaces is a significant task as it helps decrease pesticide usage and thereby reduces the risk of environmental pollution. Here, we report a method of increasing the spreading of herbicide benquitrione droplets on superhydrophobic surfaces through its selective dynamic self-assembly with amino pillar[5]arenes. Supramolecular interaction such as host-guest interaction was utilized for the complete diffusion of benquitrione over the hydrophobic plant surface. Furthermore, molecular dynamics simulations were used to verify that AP5A improved the spreading of benquitrione droplets on superhydrophobic interfaces. Moreover, complexation of benquitrione did not affect its biological activity. The present work provides a new method for improving the utilization rate of pesticides and reducing pesticide use.